Electrocatalytic Reductive Amination of Aldehydes and Ketones with Aqueous Nitrite

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

The electrocatalytic utilization of oxidized nitrogen waste for C-N coupling chemistry is an exciting research area with great potential to be adopted as a sustainable method generation organonitrogen molecules. most widely used reaction reductive amination. In this work, we develop alternative electrochemical amination that can proceed in neutral aqueous electrolyte nitrite the nitrogenous reactant and via oxime intermediate. We selection criterion reduction electrocatalysts suited electrosynthesis and, doing so, find Pd highly efficient catalyst reaction, reaching Faradaic efficiency 82% at -0.21 V vs reversible hydrogen electrode. aliphatic or aromatic structure carbonyl impacts efficacy catalyst, substrates leading suppressed formation detrimental alcohol. developed Pb/PbO electrocatalyst selectively performs electrolyte. With acetone model substrate, demonstrate one-pot, two-step conversion isopropyl amine 85% yield 50% global efficiency.

Язык: Английский

---

Spontaneous Catalytic Reaction of a Surfactant in the Interfacial Microenvironment of Colloidal Gold Nanoparticles

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(2), С. 2206 - 2215

Опубликована: Янв. 7, 2025

The performance of nanomaterials is significantly determined by the interfacial microenvironment, in which a surfactant plays an essential role as adsorbent, but its involvement reaction often overlooked. Here, it was discovered that citrate and ascorbic acid, two primarily used surfactants for colloidal gold nanoparticles (Au NPs), can spontaneously undergo catalytic with trace-level nitrogenous residue under ambient environment to form oxime, subsequently cleaved generate CN- or compound containing -CN group. Such shows wide universality both reactants, including various carbonaceous sources, metal catalysts, Au, Ag, Fe, Cu, Ni, Pt, Pd NPs. Furthermore, removal this reaction, adsorbed CO diverse adsorption configurations observed via surface-enhanced Raman spectroscopy conditions without applied potential. Our work highlights non-negligible significance microenvironments provides crucial insights into fundamental understanding chemical reactions.

Язык: Английский

---

Electrocatalytic selective synthesis and tandem utilization of hydroxylamine

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

Язык: Английский

---

Multiple active site metal-based catalysts for C-N coupling reactions and the beyond

Next Materials, Год журнала: 2025, Номер 8, С. 100555 - 100555

Опубликована: Фев. 21, 2025

Язык: Английский

---

Interfacial Asymmetrically Coordinated Zn−MOF for High‐Efficiency Electrosynthetic Oxime

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract Oximes are important intermediates for various chemicals synthesis such as pharmaceuticals, among which one vital precursor producing neurological disease, antimicrobial and anticancer agents is piperidone oxime (PDO). Compared with conventional thermocatalytic method, it's more attractive to synthesize PDO via green electrocatalytic technology especially utilizing waste nitrogen oxides gas source. However, there great challenges in catalyst design high‐efficiency electrosynthetic due the low electron transport rate multiple competing reactions. Herein, we propose an interfacial coordination strategy based on metal–organic frameworks (MOF) electrocatalyst first time promote electrosynthesis, by building Zn−O bridges between graphite felt (GF) zeolitic imidazolate framework (ZIF‐7/CGF). Specially, ZIF‐7/CGF delivers a Faraday efficiency (FE) of 75.9 % yield up 73.1 1‐methyl‐4‐piperidone oxime, far superior without (a FE 10.7 10.3 %). In‐depth mechanism study shows that introducing can transfer induce Zn sites transforming into distorted tetrahedron (Zn‐N 3 O) mode, benefits adsorption conversion. The developed presents wide universalities towards oximes electrosynthesis adapts other MOF materials (ZIF‐8, ZIF‐4). This work provides new insights organic upgrading cycle through rational surficial coordinated electrocatalysts.

Язык: Английский

---

Interfacial Asymmetrically Coordinated Zn−MOF for High‐Efficiency Electrosynthetic Oxime

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract Oximes are important intermediates for various chemicals synthesis such as pharmaceuticals, among which one vital precursor producing neurological disease, antimicrobial and anticancer agents is piperidone oxime (PDO). Compared with conventional thermocatalytic method, it's more attractive to synthesize PDO via green electrocatalytic technology especially utilizing waste nitrogen oxides gas source. However, there great challenges in catalyst design high‐efficiency electrosynthetic due the low electron transport rate multiple competing reactions. Herein, we propose an interfacial coordination strategy based on metal–organic frameworks (MOF) electrocatalyst first time promote electrosynthesis, by building Zn−O bridges between graphite felt (GF) zeolitic imidazolate framework (ZIF‐7/CGF). Specially, ZIF‐7/CGF delivers a Faraday efficiency (FE) of 75.9 % yield up 73.1 1‐methyl‐4‐piperidone oxime, far superior without (a FE 10.7 10.3 %). In‐depth mechanism study shows that introducing can transfer induce Zn sites transforming into distorted tetrahedron (Zn‐N 3 O) mode, benefits adsorption conversion. The developed presents wide universalities towards oximes electrosynthesis adapts other MOF materials (ZIF‐8, ZIF‐4). This work provides new insights organic upgrading cycle through rational surficial coordinated electrocatalysts.

Язык: Английский

---

Tuning NO coverage promotes ampere-level electrosynthesis of a nylon-6 precursor

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

The electrocatalytic synthesis of cyclohexanone oxime from NO and with high Faradaic efficiency at ampere-level current density is highly desirable but challenging. Here, theoretical calculations reveal that coverage on the Ag catalyst plays a critical role in electrosynthesis. We then adjust local concentration experimentally by tuning reaction rate. find low benefits NH₃ formation, whereas delivers N-2 (N₂O N₂) products. A mechanistic study indicates increasing coverage, active sites transfer bridge step to hollow terrace sites, which results weaker adsorption O* species, leading stable existence NH₂OH* intermediate rather than decomposing form NH₃. However, N‒N coupling also easily occurs coverage. This understanding further inspires us develop doping strategy break equivalent surface can inhibit NO–NO thus realize density. Ru-doped developed, realizing 86% 1.0 cm^{− 2}, far exceeding reported performance.

Язык: Английский

---

Intermetallic PtSn Nanosheets with p–d Orbital Hybridization for Selective Hydroxylamine Electrosynthesis

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Март 9, 2025

The electrocatalytic nitrate reduction to hydroxylamine (NH2OH) is a challenging catalytic process that has gained significant attention. However, its performance hindered by the low selectivity of electrocatalysts. Here, intermetallic PtSn nanosheets with p–d orbital hybridization have been synthesized, which significantly enhances NH2OH. Faradaic efficiency NH2OH reaches maximum 82.83 ± 1.55% at −0.10 V versus reversible hydrogen electrode (vs RHE), and yield achieves 6.15 0.32 mmol h–1 mgcat–1 −0.25 vs RHE. Mechanistic studies reveal between p-block Sn d-block Pt effectively adsorption desorption boost electrochemical synthesis. Given their excellent in synthesis NH2OH, are utilized as cathode an alkaline-acid hybrid Zn–NO3– battery facilitate production achieving FE 80.42%.

Язык: Английский

---

Surface hydroxyl on TiO2 promoted formation of α-C radical and oxaziridine intermediates in aerobic oxidation of amine into oxime

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 116111 - 116111

Опубликована: Март 1, 2025

Язык: Английский

---

Lattice Hydrogen Involved Electrocatalytic Nitrate Reduction to Hydroxylamine

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 18, 2025

Electrocatalytic nitrate reduction to hydroxylamine (ENRH) provides a sustainable strategy for NH2OH synthesis under ambient conditions. At present, active hydrogen (*H) derived from water dissociation has been widely used as H-source hydrogenation, bringing big challenge ENRH. On the one hand, insufficient *H would lead accumulation of nitrite. other sufficient with high ability induce over-hydrogenation ammonia. To overcome this challenge, herein, we propose utilize lattice (Hlat) an appropriate We design and construct Cu-MnO2Hx electrocatalyst, in which Cu-triggered Jahn-Teller distortion [MnO6] octahedron significantly increases number Hlat. The Faradaic efficiency yield are 91.1% 396.6 mmol gcat.-1 h-1 over Cu-MnO2Hx, outperforming most reported catalysts. combined results isotopic tracking experiments theoretical calculations prove enrichment buffer functions Hlat, can provide abundant nitrate's selective hydroxylamine.

Язык: Английский

---